Supramolecular Depolymerization in the Mixture of Two Poor Solvents: Mechanistic Insights and Modulation of Supramolecular Polymerization of Ionic π‐Systems

Kotha, Srinu and Mabesoone, Mathijs F. J. and Srideep, Dasari and Sahu, Rahul and Reddy, Sandeep K. and Kotagiri, Venkata Rao (2021) Supramolecular Depolymerization in the Mixture of Two Poor Solvents: Mechanistic Insights and Modulation of Supramolecular Polymerization of Ionic π‐Systems. Angewandte Chemie International Edition, 60 (10). pp. 5459-5466. ISSN 1433-7851

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Abstract

Solvents are fundamentally essential for the synthesis and processing of soft materials. Supramolecular polymers (SPs), an emerging class of soft materials, are usually stable in single and mixtures of poor solvents. In contrast to these preconceived notions, here we report the depolymerization of SPs in the mixture of two poor solvents. This surprising behavior was observed for well-known cationic perylene diimides (cPDIs) in the mixtures of water and amphiphilic organic solvents such as isopropanol (IPA). cPDIs form stable SPs in water and IPA but readily depolymerize into monomers in 50–70 vol% IPA containing water. This is due to the selective solvation of the π-surface of cPDIs by alkyl chains of IPA and ionic side chains by water, as evidenced by molecular dynamic simulations. Moreover, by systematically changing the ratio between water and amphiphilic organic solvent, we could achieve an unprecedented supramolecular polymerization both by increasing and decreasing the solvent polarity. © 2020 Wiley-VCH GmbH

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IITH Creators:

IITH Creators	ORCiD
Kotagiri, Venkata Rao	https://orcid.org/0000-0002-6821-6241

Item Type:

Article

Additional Information:

We acknowledge Prof. E. W. Meijer for fruitful discussions. K. V. R. acknowledge SERB (Grant no. ECR/2018/001222), government of India for the financial support. S. K. thanks the CSIR, India for the junior research fellowship. M. F. J. M. acknowledges NWO for funding (TOP-PUNT Grant 10018944). D. S. thanks the MHRD, government of India for the research fellowship. This work used the resources of the Supercomputing facility of Indian Institute of Technology Kharagpur established under National Supercomputing Mission (NSM), Government of India and supported by Centre for Development of Advanced Computing (CDAC), Pune. R. S. thanks the UGC, India for the junior research fellowship.

Uncontrolled Keywords:

Ionic π-systems; Molecular dynamics; Self-assembly; Solvent effects; Supramolecular polymers

Subjects:

Chemistry

Divisions:

Department of Chemistry

Depositing User:

. LibTrainee 2021

Date Deposited:

01 Oct 2022 08:26

Last Modified:

01 Oct 2022 08:26